Composition of matter and process for producing same



Patented Feb. '7', 1933 UNITED STATES PATENT OFFICE OSCAR A. CHERRY AND FRANZ KURATH, OF CHICAGO, ILLINOIS, ASSIGNOBS TO ECONOKY FUSE AND MANUFACTURING COMPANY, OF- CHICAGO, ILLINOIS, A COB- PORATIQN OF NEW YORK eourosi'rion or mrrnn am) access For. raonucma. sans It Drawing. Original application also mm. so, was, Serial No. 266,114. Divided and this application filed August 16, 1829. Serial No. 388,484.

This invention relates to a novel composition of matter and to the process of producing same, and more particularly to the. composition of matter and process characterized y reacting, in a manner to be hereinafter set forth, aldehydes, organic acids and amines.

This application is a division of the applicants Patent No. 1,800,815, issued April 14, cification appearing herein 1931, and the s is based upon t e specifi'cation of said patent. This invention, however, relates particularly to that aspect of the original disclosure having ,to" do with molding compositions comprising a phenolic condensation product in combination with reactionprodacts of carboxylic acid, aromatic amines, and aldehydes. The more specific claim to this a plication relates to the reaction product 0? stearic acid amineand furfural in combination with the phenolic condensation v roduct to form molding compositions as the urfural reaction roduct is found to possess unusually good In ricating properties.

It is known that organic acids will react with aromatic amines to form substances which in some cases are amorphous and in other cases crystalline bodies. Some of the crystalline bodies so formed possess properties which render them useful in the arts for various purposes, whereas the amorphous substances referred to or thosebodies which 1 are difiicultly crystallizable, have received no extended commercial application.

It is further knownthataldehydes suchas, for instance, formaldehydes .or furfural, will react with aromatic amines under favorable conditions to form amor hous or resin ous bodies, which resinous" cially.

It has now been found that by reactin with aldeh des on the reaction products 0 certain car oxylic acids and aromatic pri-' mary amines that products possessing considerable utility may be obtained.- These products may be amorphous, or resinous, brittle, or may possess considerable tenacity, dependin upon the particular combination of aldehy e, acid and amine selected.

I odies or sub stances have been of only little use commere molding operations.

The present invention accordingly roceeds upon the principle of reacting a dehydes, acids and amines to form compositions of matter which are new and useful in different products, but it is to be understood,

that the invention is to be construed broadly enough to include, the group of products produced by reacting the substances in a general manner falling within the scope of this invention, it being, of course, understood that the particular examples given herein are merely by way of illustration, and are ones which represent the preferred forms of practicing the invention. s

. As above stated, the variations whichmay be made inthe process and product are numerous inthat different amines'may be used to react with a particular selection of acid.

and aldehyde, or different acids may be used in connection with a particular aldehyde and amine, or different-aldehydes may be used to react with a particular acid amlne reaction product. It is also within the contemplation of the present invention to employ instead of pure compounds, a mixture of oneor more 1 of the compounds enumerated, such as, for instance, mixturesof different acids, amines or aldehydes in any desirable combination for the purpose of obtaining the particular properties desired in the final roduct.

' It has also been found, as will be hereinafter more particularly pointed out, that some of the products falling within the group contemplated in the present invention, are waxy substances ossessing'many of the physical properties o natural waxes.

Accordingly, it is one of the objects of the.

present invention to provide a new composition of matter or group of substances possessing new and useful properties.

It is also an object of this invention to provide a plasticizing agent forpotentially'reactive phenolic condensation products in hot It is a further object of this invention to rovide a hot molding composition com r1smg a phenolic condensation product an one of a group of substances, WhlCh possess prop erties suitable for use as plasticizmg agents as above set forth, which possess either the property of a plasticizing agent, or a lubricant for use in hot molding operations, or of a sub stance for darkening molding phenolic condensation products, or any combination, or 'all of these properties.

Various other objects of this invention will appear as the description proceeds.

In order that the invention may be more readily understood, various examples will be given herein of the process and product contemplated and inasmuch as a variety of each of the substances or compounds, viz, the aldehydes, acids and amine, is contemplated in practicing the present invention, it is deemed advisable to group these and treat them separately as typical examples.

Irrespective of the particular selection of compounds, it is to be understood that in all cases the aldehyde is reacted with the reaction product of the acid and amine, or, in other words, the acid and amine are reacted initially and the product thereof is subsequently reacted with the aldehyde.

The first group of examples are those in which various aldehydes are used. lhe first example of the group is as follows: In a flask equipped with a return condenser, 56.8 parts by weight of stearic acid and 18.6 parts by weight of aniline are heated to substantially from 170 to 200 C. for approximately one hour. \Vater is formed as a result of the reaction between the organic acid and the amine. In order to eliminate the water so formed, it is desirable to so arrange the condenser that the water may escape, but so that any aniline being volatized will be returned to the flask. At the end of the heating period, and after some cooling, 19 parts by weight of furfural are added and the whole is heated to about 200 C. for approximately one-half hour. At this temperature the product is a thin liquid, which, upon cooling, solidifies to a waxy, dark brown solid at room temperature. The product so formed is a substitute for natural waxes and is found suitable to replace them in man of their applications, and is especially valirable for use in phenolic condensation products, particularly hot molding compositions made from potentially reactive phenolic condensation products.

The product formed in accordance with the above process is found, when used with hot molding compositions as above referred to,

to have a three-fold function. The waxy product first serves to lubricate the composition in such a manner as to prevent sticking of the composition to the steel molds in which these compositions are ordinarily molded. This is a decidedly valuable property espec' ially in connection with certain compositions made in part from furfural, which compositions have a tendency to stick to the mold during hot pressing operations. The above product secondly serves to plasticize the phenolic hot molding compositions, causing the materials to flow more readily during the molding operations; and, thirdly, they serve in such compositions to darken to some extent the final product.

A second example which is somewhat similar to that above given, with the exception that the furfural is replaced by formaldehyde, produces a product somewhat similar to that above described, with the exception that it does not afl'ect the color of the products in which it is dissolved or mixed, but generally speaking, it may be used in the same way as the furfural product, it possessing the lubricating and plasticizing properties. This product is produced by replacing the furfural in the above stated example by 15 parts by weight (M commercial formaldehyde solution. On account of the water in the formaldehyde, the heat treating temperature is necessarily less, and about one hour is usually required to eflect complete combination of'the aldehyde. The product so obtained is similar to the furfural product, but is a trifle more brittle and is light in color.

A condensing agent, as for example a mineral acid, may be employed to accelerate the reaction between the aldehyde and the amine acid compound. \Vhcn furfural is the alde-.

hyde employed, the use of an acid catalyst serves to make the resultant composition of a very deep, black color.

The next examples which are to follow are those in which acids other than stearic acid are used with aniline in substantially the same procedure as that given above. The products which result from the employment of the various acids are found to possess slightly varying properties, depending upon the acid selected, and to a lesser extent upon the aldehyde. For example, succinic acid may be employed in the reaction with aniline and furfural and is found to yield a black, viscous mass, possessing no waxy properties. Benzoic acid, aniline and furfural yield a black product, which is quite tough and somewhat plastic at ordinary temperatures.

By reacting a mixture of benzoic and stearic acids in equi-molecular proportions upon a double molecular proportion of aniline, and by reacting the product with furfural, a black, waxy mass is obtained. This product is somewhat tougher and more plastic than a similar product made from stearic acid alone. By reducing the proportions of benzoic acid in the above mixture, the hardness and the waxlike nature of the product is increased. Oleic acid, aniline and furfural yield a black, viscous, oleaginous product. lVhen'the product of a mixture of oleic and stearic acids reacted and continuing the heat treatment. T e reaction of the rosin-aniline substance with formaldehyde is so violent that if formaldehyde is to be reacted with this substance the solution is to be added slowly in small increments. The rosin-amine-aldehyde product so formed is resinous as is rosin, but is less brittle than rosin. It has a decided plasticizing action on reactive phenolic molding compositions, such as are used in hot molding operations. It is found that by replacing about one-half of the rosin in the above reaction by stearic acid and forming a mixed acid-amine-aldehyde product, a substance possessing both resinous and wax-like characteristics may be obtained.

The examples hereinafter given will be illustrative of the results obtained when various amines are employed. It is found in practice that by using a diamine and by using mixtures of acids as well as single acids, a variety of products may be obtained. The products are in general harder at room temperatures than similar compounds made from simple amines. For example, a hard, wax-like product is obtained by reacting upon one gram mol of meta-phenylene-diamine with one gram mol 1 of benzoic acid and one gram mol of stearic acid, and treating the product with two gram mols of furfural. A black, high melting waxlike substance, not uite so tough as that ohtainable as above escribed, ma be made from one gram mol of stearic aci one gram mol of metaphenylene diamine and one gram mol of furfural. A lower melting substance may be made by increasing the proportions of stearic acid in the above example.

Other amines, such as toluidines and naphthylamines may be used. The carboxylic acids of high molecular weights, that is, those acids containing more than 6 carbon atoms are preferred, as acids of lower molecular weight usually produce crystalline derivatives with aniline. Although there is nothing objectionable per se in a crystalline intermediate product useful products are generally more easily obtainable from acids of higher molecular weight. In fact, some of the very low molecular weight acids, as for example acetic acid, do not react with aniline to form a product which will easily react with aldehydes.

We claim:

1. A molding composition comprising a potentially reactive phenolic condensation product and the reaction product of carboxylic acid, aromatic amines and aldehydes.

2. A molding composition comprising a potentially reactive phenolic condensation product and the reaction productof furfural on the reaction product of carboxylic acid and aromatic amines.

3. A molding composition comprising a potentially reactive phenolic condensation product and the product formed by reacting furfural on the reaction product of stearic acid and aromatic amines.

4. A molding composition comprising a potentially reactive phenolic condensation product and the product formed by reacting furfural on the reaction product of 'stearic acid and aromatic amines and aniline.

5. A molding composition comprising a potentially reactive phenolic condensation product and a product formed by reacting furfural on the reaction product of carboxylic acids and aniline.

Signed at Chicago, Illinois, this 12th day of August, 1929. x

' OSCAR A. CHERRY.

FRANZ KURATH 

